Organoclay compositions

ABSTRACT

Organoclay compositions which comprise the reaction product of a smectite-type clay having an ion exchange capacity of at least 50 meq. wt. per 100 g. clay (active basis), and an alkoxylated quaternary ammonium compound having one or two alkoxylated chains containing 0-10 moles ethylene oxide and 3-15 moles of propylene or butylene oxide residues are useful thixotropic materials, especially for the preparation of aqueous systems.

BACKGROUND OF THE INVENTION

This invention relates generally to organoclays, and, more specifically,to improved organoclays which are produced by the reaction of theorganoclay with an alkoxylated quaternary ammonium compound.

Organoclays, representing the reaction product of a smectite-type daywith a quaternary ammonium compound, have long been known for use ingelling of organic liquids such as lubricating oils, linseed oil,toluene and the like. A large variety of highly useful products, such aslubricating greases, are producible through use of such gelling agents.The procedures and chemical reactions pursuant to which theseorganoclays are prepared, are well-known. Thus, under appropriateconditions, the organic compound which contains a cation, will react byion exchange with the clay which contains a negative layer lattice andexchangeable cations to form the organoclay products.

Other uses for such modified organoclays are those such as are disclosedin U.S. Pat. No. 5, 151,155, wherein organically modified smectite claysare utilized in a process for deinking wastepaper, and in U.S. Pat. No.4,677,158, wherein smectite-type clays which have been reacted withquaternary ammonium compounds are utilized as thickeners for aqueoussuspensions, particularly latex paints and caulks. These modifiedorganoclays differ from those of the present invention in the type ofquaternary ammonium compound with which they are reacted. Thismodification produces organoclays with markedly superior properties thanthose of the prior art.

OBJECTS OF THE INVENTION

It is an object of the present invention to prepare organoclaycompositions having improved rheological properties, and thus useful asthixotropes in aqueous compositions.

It is further an object of the present invention to prepare improvedaqueous compositions, especially paint formulations, which possessimproved properties by virtue of their inclusion of the organoclaycompositions of the present invention.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has unexpectedly beendiscovered that the reaction of smectite-type clays with certainalkoxylated quaternary ammonium compounds can produce organoclayproducts having superior properties when utilized as water-basedthixotropes.

Thus, the present invention is concerned with an organoclay compositioncomprising the reaction product of a smectite-type clay having an ionexchange capacity of at least 50 meq. wt. per 100 g. clay (activebasis), and an alkoxylated quaternary ammonium compound having thefollowing formula: ##STR1## wherein R₁ and R₂ are alike or different,and are selected from the group consisting of C₁ -C₈ alkyl, benzyl or2-hydroxyethyl groups; R₃ is a C₁ -C₈ alkyl, benzyl or 2-hydroxyethylgroup, or an alkoxylated chain containing 0-10 moles ethylene oxide and3-15 moles of an alkylene oxide residue selected from the groupconsisting of propylene oxide, butylene oxide, and mixtures thereof; andR₄ is an alkoxylated chain containing 0-10 moles ethylene oxide and 3-15moles of an alkylene oxide residue selected from the group consisting ofpropylene oxide, butylene oxide, and mixtures thereof; and X is the saltanion.

DESCRIPTION OF PREFERRED EMBODIMENTS

The smectite clays which are utilized as one of the starting materialsof the present invention are those which have been conventionallyutilized in the prior art. Suitable smectite-type clays are those whichhave a cation exchange capacity of at least 50 milliequivalents (meq.)weight (wt.) per 100 grams of clay (active basis). Useful clays for suchpurposes include the naturally occurring Wyoming variety of swellingbentonite and similar clays, and hectorite, which is a swellingmagnesium-lithium silicate clay. The clays are preferably converted tothe sodium form if they are not already in this form. This can beeffected, again as in known in the art, by a cation exchange reaction,or the clay can be converted via an aqueous reaction with a solublesodium compound.

Smectite-type clays prepared synthetically can also be utilized, such asmontmorillonite, bentonite, beidelite, hectoritesaponite, andstevensite. Such clays, and processes for their preparation, aredescribed in U.S. Pat. Nos. 4,695,402, 3,855,147, 3,852,405, 3,844,979,3,844,978, 3,671,190, 3,666,407, 3,586,478, and 3,252,757, all of whichare herein incorporated by reference.

The alkoxylated quaternary ammonium salts which are reacted with thesmectite-type clay are of the formula ##STR2## wherein R₁ and R₂ arealike or different, and are selected from the group consisting of C₁ -C₈alkyl, benzyl or 2-hydroxyethyl groups; R₃ is a alkyl, benzyl or2-hydroxyethyl group, or an alkoxylated chain containing 0-10 molesethylene oxide and 3-15 moles an alkylene oxide residue selected fromthe group consisting of propylene oxide, butylene oxide and mixturesthereof; and R₄ is an alkoxylated chain containing 0-10 moles ethyleneoxide and 3-15 moles of an alkylene oxide residue selected from thegroup consisting of propylene oxide, butylene oxide and mixturesthereof; and X is the salt anion.

The salt anion X is methosulfate, ethosulfate, methylcarbonate,ethylcarbonate, chloride, bromide, or mixtures thereof, and is mostpreferably a methosulfate ion. The salt anion may also, however, benitrate, hydroxide, acetate, or mixtures of these.

The alkoxylated chains present in the alkoxylated quaternary ammoniumcompounds of the present invention determine the particularlyadvantageous properties of the resultant organoclays of the presentinvention. Thus, the prior art organoclays which contain saturated alkylgroups in the quaternary ammonium compound provide modified organoclayswhich are too hydrophobic to be useful in aqueous systems. Likewise, theuse of the prior art polyethoxylated chain quaternary ammonium compoundsprovide modified organoclays which are too hydrophilic and which provideorganoclays which are difficult to de-water during processing steps. Itis thus critical to the present invention to provide quaternary ammoniumcompounds which, upon reaction with the smectite-type clay, will affordan organoclay composition having the desired hydrophobic/hydrophilicbalance, resulting in desirable properties in the end-products.

Preferred embodiments of the present invention will utilize quaternaryammonium compounds having one or two alkoxylated chains each containing1-5 moles ethylene oxide and 4-10 moles propylene oxide and/or butyleneoxide residues.

Highly preferred embodiments of the present invention are organoclayswhich comprise the reaction product of smectite-type clays withalkoxylated quaternary ammonium compounds wherein the R₃ and R₄ chainseach contain the residue of 5 moles ethylene oxide and 5 moles propyleneoxide, and are thus represented by the following formula:

    (CH.sub.3).sub.2 N[(CH.sub.2 CH.sub.2 O).sub.x (CH.sub.2 CH(CH.sub.3)O.sub.y ].sub.2 H

wherein

x and y=5

or wherein

R₃ and R₄ each contain the residue of 1 mole of ethylene oxide and 4moles of propylene oxide, represented by the formula:

    (CH.sub.3).sub.2 N[(CH.sub.2 CH.sub.2 O).sub.x (CH.sub.2 CH(CH.sub.3)(O).sub.y ].sub.2 H

wherein

x and y=4

or wherein

R₃ and R₄ each contain the residue of 1 mole ethylene oxide and 5 moleseach of propylene oxide and butylene oxide, represented by the formula:

    (CH.sub.3).sub.2 N[(CH.sub.2 CH.sub.2 O).sub.x (CH.sub.2 CH(CH.sub.3)O).sub.y (CH.sub.2 CH(CH.sub.2 CH.sub.3)O).sub.z ].sub.2 H

wherein

x=1, y=5 and z=2

Other preferred embodiments of the invention involve the reactionproduct of a smectite-type clay with an alkoxylated quaternary ammoniumcompound wherein R₁. R₂ and R₃ are each a methyl group and R₄ is analkoxylated chain containing 1 mole ethylene oxide and 9 moles propyleneoxide represented by the formula:

    (CH.sub.3).sub.3 N[(CH.sub.2 CH.sub.2 O).sub.x (CH.sub.2 CH(CH.sub.3)O).sub.y ]H

wherein

x=1 and y=9

or when

R₄ is an alkoxylated chain containing 1 mole ethylene oxide, 5 molespropylene oxide and 5 moles of butylene oxide represented by theformula:

    (CH.sub.3).sub.3 N[(CH.sub.2 CH.sub.2 O).sub.x (CH.sub.2 CH(CH.sub.3)O).sub.y (CH.sub.2 CH(CH.sub.2 CH.sub.3)O).sub.z ]H

wherein

x=1, y=5 and z=5.

x, y and z when employed herein denote relative reactive molar ratiosand the reaction products generally represent a product distributioncentered around these ratios.

Other quaternary ammonium salts which are particularly useful in thepresent invention are described in the U.S. Pat. Nos. 3,123,641,4,144,122, 4,432,833 and 5,296,627, which are incorporated herein byreference.

The alkoxylated quaternary ammonium compounds useful in the presentinvention of the present invention can be prepared by various methodsknown by those of ordinary skill in the art. In a preferred method, thequaternary ammonium compound is prepared by the reaction of a tertiaryamine and an alkylating agent. Some alkylating agents, well known tothose practicing the art, include organic halides such as methylchloride, diorganosulfates such as dimethyl sulfate, or diorganocarbonates, such as dimethyl carbonate. This method of preparation isdescribed in ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY edited by Kirk/Othmer(Third Edition, Vol 19, page 521-531) which is incorporated herein byreference.

The tertiary amine, useful in preparing the quaternary ammonium salt, ispreferably a polyalkoxylated amine produced by reacting ammonia, aprimary amine, or a secondary amine with an alkoxylating agent. Suitablealkoxylating agents include alkyl epoxides such as ethylene oxide,propylene oxide, and butylene oxide. Tertiary polyalkoxylated amineswhich can also be employed in the present invention are prepared byreacting ammonia, a primary amine, or a secondary amine with apolyalkoxylated alcohol or polyakoxylated glycol. Especially usefultertiary amines may also be made by alkylating a primary, or secondaryalkoxylated amine, such as the available JEFFAMINE® series ofalkoxylated amines available from Huntsman Chemicals (JEFFAMINE® is aregistered mark of Huntsman Chemicals Inc.) or the available TECTRONIC®series of alkoxylated amines available form BASF Corporation (TECTRONIC®is a registered trademark of BASF Corporation). Examples of othertertiary amines useful in the present invention can be found in U.S.Pat. Nos. 3,654,370, 4,739,094, 4,960,942, 4,967,005, 5,344,984 and5,347,051, which are incorporated herein by reference.

The amount of the alkoxylated quaternary ammonium compound reacted withthe smectite-type clay depends upon the specific clay and the desireddegree of hydrophobicity. Typically, the amount of cation ranges fromabout 0.1 to about 150%, preferably from about 100 to about 130% of thecation exchange capacity of the clay. Thus, for example, when bentoniteis used, the amount of cation reacted with the clay will range fromabout 85 to about 143 milliequivalents, preferably from about 95 toabout 124 milliequivalents per 100 grams of clay, 100% active basis.

A further embodiment of the present invention is the process forpreparing the organoclay composition comprising the reaction product ofa smectite-type clay having an ion exchange capacity of at least 50 meq.wt. per 100 g. clay (active basis), and an alkoxylated quaternaryammonium compound of the formula: ##STR3## wherein R₁ and R₂ are alikeor different, and are selected from the group consisting of C₁ -C₈alkyl, benzyl or 2-hydroxyethyl groups; R₃ is a C₁ -C₈ alkyl, benzyl or2-hydroxyethyl group, or an alkoxylated chain containing 0-10 molesethylene oxide and 3-15 moles an alkylene oxide residue selected fromthe group consisting of propylene oxide, butylene oxide and mixturesthereof; and R₄ is an alkoxylated chain containing 0-10 moles ethyleneoxide and 3-15 moles of an alkylene oxide residue selected from thegroup consisting of propylene oxide, butylene oxide and mixturesthereof; and X is the salt anion; which comprises:

a) dispersing a smectite type clay having an ion exchange capacity of atleast 50 meq. wt. per 100 g. clay in an aqueous media;

b) heating the dispersing of step (a) to a temperature in excess of 30°C.;

c) adding the heated dispersion of step (b) of a quaternary ammoniumsalt of the formula ##STR4## wherein R₁ and R₂ are alike or different,and are selected from the group consisting of C₁ -C₈ alkyl, benzyl or2-hydroxyethyl groups; R₃ is a C₁ -C₈ alkyl, benzyl or 2-hydroxyethylgroup, or an alkoxylated chain containing 0-10 moles ethylene oxide and3-15 moles an alkylene oxide residue selected from the group consistingof propylene oxide, butylene oxide and mixtures thereof; and R₄ is analkoxylated chain containing 0-10 moles ethylene oxide and 3-15 moles ofan alkylene oxide residue selected from the group consisting ofpropylene oxide, butylene oxide and mixtures thereof; and X is the saltanion, in the desired milliequivalent ratio; and

d) agitating the mixture of step (c) to effect completion of thereaction.

The organoclay composition of the present invention is thus prepared byadmixing an aqueous dispersion of the smectite-type clay, warmed to atemperature in excess of 30° C., with an alkoxylated quaternary ammoniumcompound of formula I to exchange the metal counterions that arenaturally present in the smectite-type clay. The reaction is typicallyconducted at a temperature within the range of from about 40° C. toabout 100° C. for a period of time sufficient for the alkoxylatedquaternary ammonium compound to react with the clay particles.

Preferably, the clay is dispersed in the water at a concentration fromabout 3% to about 15% by weight and the slurry is centrifuged to removenon-clay impurities. The slurry is then agitated and heated to thedesired temperature, and the quaternary ammonium salt added in thedesired milliequivalent ratio. The alkoxylated quaternary ammoniumcompounds are typically liquids, but they can be dispersed in water tofacilitate the reaction. Agitation is continued to effect completion ofthe reaction.

The mount of the alkoxylated quaternary ammonium compound added to thesmectite-type clay for the purposes of this invention must be sufficientto impart to the clay the enhanced characteristics desired. Themilliequivalent ratio is defined as the number of milliequivalents ofthe alkoxylated quaternary ammonium compound, per 100 grams of clay,100% active basis. The typical smectite-type days of this invention havea milliequivalent ratio of from about 10 to about 150. The preferredmilliequivalent ratio will vary depending on the characteristics of theparticular alkoxylated quaternary ammonium compound utilized and the enduse for the resultant product.

When the organoclay composition of the present invention is utilized forits rheological properties for application as to control sagging offluid films and prevent settling and hard packing of pigments present inpaint compositions, particularly latex paint compositions, it istypically employed in an amount of about 5 lb. to about 95 lb./100gallons paint composition.

The present invention thus contemplates the preparation of latex paintformulations having improved properties which comprise the addition ofthe improved organoclay composition which is the reaction product of asmectite-type clay having an ion exchange capacity of at least 50 meq.wt. per 100 g. clay and an alkoxylated quaternary ammonium compound ofthe general formula I. Typically, the latex paint formulation willcontain the improved organoclay composition is an amount of about 2 toabout 10% by weight of the finished latex paint formulation. Preferredformulations contain the organoclay thixotrope in an amount of about 3to about 6% by weight of the finished latex paint formulation.

Latex paint formulations containing the organoclay composition of theinstant invention exhibit superior characteristics when brush out, rollout and spray out applications were compared with standard commerciallyavailable latex paint formulations. The latex paints formulated usingthe organoclay compositions exhibited a high low-shear viscosity and alow high-shear viscosity in contrast to the commercial paints whichexhibited lower low-shear values and higher high-shear values. Whensheared, theses latex paint formulations thinned out to a flowable andworkable viscosity. The low high-shear viscosity of the these latexpaints results in excellent atomization in airless spray application. Inaddition, the presence of the organoclay in the latex paint formulationsimproved the sag characteristics of these paints to such a degree thatsprayouts of thirty mils or higher were common.

The invention will now be illustrated by a series of Examples, which areintended to set forth typical and preferred procedures to be utilized inthe practice of the invention.

EXAMPLE 1

The preparation of a smectite-type clay composition comprising thereaction product of a smectite-type clay and a quaternary ammoniumcompound of the formula I wherein the R₁ and R₂ are each a methyl groupand the R₃ and R₄ chains each contain the residue of 5 moles ethyleneoxide and 5 moles propylene oxide is prepared as follows:

5000 Grams of an aqueous three pass slurry of montmorillonite SCPX 818containing 3.72 % solids in a 5 gallon tank is heated on a lighteningmixer to 60° C. (140° F.). To this heated slurry is then added 87.19grams of the alkoxylated quaternary ammonium compound of formula Iwherein the R₁ and R₂ are each a methyl group and the R₃ and R₄ chainseach contain the residue of 5 moles ethylene oxide and 5 moles propyleneoxide (AKR 94005 Lot #94016RS-T) at 30 MER, which mixture is thenstirred for fifteen minutes until the clay swells and mixing is nolonger possible. After transfer to a quart jar, no separation wasobserved after twenty-four hours, indicating completion of the reaction.

This was calculated 5.03% solids 255.89 grams dry clay

EXAMPLE 2

The preparation of a smectite-type clay composition comprising thereaction product of a smectite-type clay and a quaternary ammoniumcompound of the formula I wherein the R₁ and R₂ are each a methyl groupand the R₃ and R₄ chains each contain the residue of 1 mole ethyleneoxide and 5 moles propylene oxide is prepared as follows:

5000 Grams of an aqueous three pass slurry of montmorillonite SCPX 818containing 3.72% solids in a 5 gallon tank is heated on a lighteningmixer to 60° C. (140° F.). To this heated slurry is then added 43.6grams of the alkoxylated quaternary ammonium of formula I wherein the R₁and R₂ are each a methyl group and the R₃ and R₄ chains each contain theresidue of 1 mole ethylene oxide and 5 moles propylene oxide (ARK 94006Lot #94016RS-T) at 20 MER, which mixture is then stirred for fifteenminutes until the clay swells and mixing is no longer possible. Aftertransfer to a quart jar, no separation was observed after twenty-fourhours, indicating completion of the reaction.

This was calculated 4.38% solids 220.91 grams dry clay

EXAMPLE 3

A latex paint formulation consisting of:

    ______________________________________                                        Volume   Material             Weight                                          ______________________________________                                        5.85     SM/OC CEP/HRD Thixotrope prepared                                                                  49.70                                                    as in Example 1                                                      14.42    Water                120.30                                          0.09     Troysan 142-Bacteriostat                                                                           1.00                                            0.65     Tamol 731            6.00                                            0.05     Potassium Tripolyphosphte                                                                          1.00                                            0.34     Triton N-101         3.00                                            0.13     AMP-95               1.00                                            2.55     Propylene Glycol     22.00                                           0.27     Bubble Breaker 748   2.00                                            Procedure for preparation: Add together the following and mix:                5.09     T1O2 CR-800          175.00                                          4.42     No. 1 White          100.00                                          3.56     Snowflake White      80.00                                           7.99     ECCA Tex 90          175.00                                                   Disperse to 5 + Hegman                                                        3400 RPM, 15 m. Dispermat                                            16.61    Water                138.50                                          0.27     Bubble Breaker 748   2.00                                            5.85     SM/OC CEP/HRD Tbixotrope prepared                                                                  49.70                                                    as in Example 1                                                      1.14     Texanol              9.00                                            Then, mix and add:                                                            31.27    UCAR 376 Latex       283.00                                                 Check the following specs:                                                    Viscosity, KU                                                                             95                                                                ICI, Poise  0.8                                                               BF 1        66,800                                                            10          10,520                                                            100         1,904                                                             Leneta Sag  12                                                                Leneta Leveling                                                                           3                                                                 Final pH    8.16                                                              Weight/Gallon                                                                             11.95                                                             Syneresis 120/10D                                                                         1-2%                                                              Syneresis Ambient                                                                         --                                                         ______________________________________                                    

EXAMPLE 4

A latex paint formulation consisting of:

    ______________________________________                                        Volume   Material             Weight                                          ______________________________________                                        8.19     SM/OC CEP/HRD Thixotrope prepared                                                                  69.58                                                    as in Example 1                                                      12.04    Water                100.42                                          0.09     Troysan 142-Bacteriostat                                                                           1.00                                            0.65     Tamol 731            6.00                                            0.05     Potassium Tripolyphosphte                                                                          1.00                                            0.34     Triton N-101         3.00                                            0.13     AMP-95               1.00                                            2.55     Propylene Glycol     22.00                                           0.27     Bubble Breaker 748   2.00                                            Procedure for preparation: Add together and mix the following:                5.09     T1O2 CR-800          175.00                                          4.42     No. 1 White          100.00                                          3.56     Snowflake White      80.00                                           7.99     ECCA Tex 90          175.00                                                   Disperse to 5 + Hegman                                                        3400 RPM, 15 m. Dispermat                                            14.22    Water                118.62                                          0.27     Bubble Breaker 748   2.00                                            8.19     SM/OC CEP/HRD Thixotrope prepared                                                                  69.58                                                    as in Example 1                                                      1.14     Texanol              9.00                                            Then, mix and add:                                                            31.27    UCAR 376 Latex       283.00                                                 Check the following specs:                                                    Viscosity, KU                                                                             126                                                               ICI, Poise  1.0                                                               BF 1        82,000                                                            10          28,100                                                            100         5,710                                                             Leneta Sag  724                                                               Leneta Leveling                                                                           1                                                                 Final pH    8.14                                                              Weight/Gallon                                                                             11.96                                                             Syneresis 120/10D                                                                         1-2%                                                              Syneresis Ambient                                                                         --                                                         ______________________________________                                    

EXAMPLE 5

A latex paint formulation consisting of:

    ______________________________________                                        Volume   Material             Weight                                          ______________________________________                                        5.40     SM/OC CEP/HRD Thixotrope prepared                                                                  45.66                                                    as in Ex. 2                                                          14.91    Water                124.34                                          0.09     Troysan 142-Bacteriostat                                                                           1.00                                            0.65     Tamol 731            6.00                                            0.05     Potassium Tripolyphosphte                                                                          1.00                                            0.34     Triton N-101         3.00                                            0.13     AMP-95               1.00                                            2.55     Propylene Glycol     22.00                                           0.27     Bubble Breaker 748   2.00                                            Procedure for preparation: Add the following ingredients together and         mix:                                                                          5.09     T1O2 CR-800          175.00                                          4.42     No. 1 White          100.00                                          3.56     Snowflake White      80.00                                           7.99     ECCA Tex 90          175.00                                                   Disperse to 5 + Hegman                                                        3400 RPM, 15 m. Dispermat                                            17.09    Water                142.54                                          0.27     Bubble Breaker 748   2.00                                            5.40     SM/OC CEP4M Thixotrope prepared                                                                    45.66                                                    as in Ex. 2                                                          1.14     Texanol              9.00                                            Then, mix and add:                                                            1.27     UCAR 376 Latex       283.00                                                 Check the following specs:                                                    Viscosity, KU                                                                             94                                                                ICI, Poise  0.8                                                               BF 1        68,800                                                            10          11,560                                                            100         2,028                                                             Leneta Sag  12                                                                Leneta Leveling                                                                           3-4                                                               Final pH    8.19                                                              Weight/Gallon                                                                             11.96                                                             Syneresis 120/10D                                                                         1-2%                                                              Syneresis Ambient                                                                         --                                                         ______________________________________                                    

EXAMPLE 6

A latex paint formulation consisting of the following:

    ______________________________________                                        Volume   Material             Weight                                          ______________________________________                                        8.11     SM/OC CEP/HRD Thixotrope prepared                                                                  68.49                                                    in Ex. 2                                                             12.17    Water                101.51                                          0.09     Troysan 142-Bacteriostat                                                                           1.00                                            0.65     Tamol 731            6.00                                            0.05     Potassium Tripolyphosphte                                                                          1.00                                            0.34     Triton N-101         3.00                                            0.13     AMP-95               1.00                                            2.55     Propylene Glycol     22.00                                           0.27     Bubble Breaker 748   2.00                                            Procedure for preparation: Add the following together and mix:                5.09     TIO2 CR-800          175.00                                          4.42     No. 1 White          100.00                                          3.56     Snowflake White      80.00                                           7.99     ECCA Tex 90          175.00                                                   Disperse to 5 + Hegman                                                        3400 RPM, 15 m. Dispermat                                            14.35    Water                119.71                                          0.27     Bubble Breaker 748   2.00                                            8.11     SM/OC CEP/HRD Thixotrope prepared                                                                  68.49                                                    in Ex. 2                                                             1.14     Texanol              9.00                                            Then, mix and add:                                                            31.27    UCAR 376 Latex       283.00                                                 Check the following specs:                                                    Viscosity, KU                                                                             102                                                               ICI, Poise  0.9                                                               BF 1        72,400                                                            10          16,400                                                            100         3,076                                                             Leneta Sag  16                                                                Leneta Leveling                                                                           2                                                                 Final pH    8.17                                                              Weight/Gallon                                                                             11.95                                                             Syneresis 120/10D                                                                         1-2%                                                              Syneresis Ambient                                                                         --                                                         ______________________________________                                    

EXAMPLE 7

A latex paint formulation consisting off

    ______________________________________                                        Volume   Material             Weight                                          ______________________________________                                        20.00    SM/OC CEP/HRD Thixotrope prepared                                                                  170.00                                                   as in Example 2                                                      0.09     Troysan 142-Bacteriostat                                                                           1.00                                            0.65     Tamol 731            6.00                                            0.05     Potassium Tripolyphosphte                                                                          1.00                                            0.23     Triton N-101         2.00                                            0.13     AMP-95               1.00                                            2.55     Propylene Glycol     22.00                                           0.27     Bubble Breaker 748   2.00                                            Procedure for preparation: Add together the following and mix:                5.47     T1O2 CR-813          175.00                                          4.42     No. 1 White          100.00                                          7.99     Satintone white      17500                                           3.46     Minex 7              75.00                                                    Disperse to 5 + Hegman                                                        3400 RPM, 15 m. Dispermat                                            1.73     Water                14.40                                           0.27     Bubble Breaker 748   2.00                                            20.00    SM/OC CEP/HRD Thixotrope prepared                                                                  170.00                                                   as in Ex. 2                                                          1.14     Texanol              9.00                                            Then, mix and add:                                                            31.27    UCAR 376 Latex       283.00                                          ______________________________________                                    

EXAMPLE 8

A latex paint formulation consisting of:

    ______________________________________                                        Volume   Material             Weight                                          ______________________________________                                        40.00    SM/OC CEP/HRD Thixotrope prepared                                                                  340.00                                                   as in Example 2                                                               Thixotrope load adjusted on                                                   a dry solids basis                                                            (Thix. + water = 170.0 grams)                                        0.09     Troysan 142-Bacteriostat                                                                           1.00                                            0.65     Tamol 731            6.00                                            0.05     Potassium Tripolyphosphte                                                                          1.00                                            0.34     Triton N-101         3.00                                            0.13     AMP-95               1.00                                            2.55     Propylene Glycol     22.00                                           0.27     Bubble Breaker 748   2.00                                            Procedure for preparation: Add together the following and mix:                5.09     T1O2 CR-800          175.00                                          4.42     No. 1 White          100.00                                          3.56     Snowflake white      80.00                                           7.99     ECCA TEX 90          175.00                                                   Disperse to 5 + Heginan                                                       3400 RPM, 15 m. Dispermat                                            2.18     Water                18.20                                           0.27     Bubble Breaker 748   2.00                                            1.14     Texanol              9.00                                            Then, mix and add:                                                            31.27    UCAR 376 Latex       283.00                                          ______________________________________                                    

EXAMPLE 9 Comparison of Paint Formulations

A. An aqueous slurry of non-exchanged montmorillonite added to paint ata rate of 6 dry lbs/100 gallons paint was found to have the followingcharacteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     94,400 cps.                                                10 RPM             17,880 cps.                                                100 RPM             2,884 cps.                                                Krebs Stormer Viscosity                                                                          99 KU                                                      ICI Cone and Plate Viscosity                                                                     0.9                                                        Leneta Chart                                                                  Sag Reading        10                                                         Leveling Reading   30                                                         pH                 8.55                                                       Temp. °C.   23.6                                                       Pounds/Gallons     11.90 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.63                                                       Scrub rating        94/152                                                                       106/152                                                    Brush Drag Rating  2.5-3                                                      Brush Out Rating   Good Loading                                                                  Poor Leveling                                              Roller Splatter Rating                                                                           6                                                          Spray Out Rating   Good Atomization at 12-14 mil.                             Roll Out Rating    2 Splatter                                                                    Fine Texture                                               ______________________________________                                    

B. An aqueous slurry of montmorillonite exchanged with the quat ACAR94005 (prepared as in Example 1, at 30 milliequivalence/100 gramsmontmorillonite) added to the same paint as A at 7 dry lbs/100 gallonspaint was found to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     80,000 cps.                                                10 RPM             14,400 cps.                                                100 RPM             2,628 cps.                                                Krebs Stormer Viscosity                                                                          97 KU                                                      ICI Cone and Plate Viscosity                                                                     0.8                                                        Leneta Chart                                                                  Sag Reading        8                                                          Leveling Reading   4                                                          pH                 8.57                                                       Temp. °C.   23.7                                                       Pounds/Gallons     11.92 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.2                                                        Scrub Rating       115/188                                                                       148/211                                                    Brush Drag Rating  2                                                          Brush Out Rating   Good Loading                                                                  Poor Leveling                                              Roller Splatter Rating                                                                           6-7                                                        Spray Out Rating   Good Atomization at 20 mils.                               Roll Out Rating    5 Splatter                                                                    Med Texture                                                ______________________________________                                    

C. An aqueous slurry of montmorillonite exchanged with the quat ACAR94006 (prepared as in Example 2 at 20 milliequivalence/100 gramsmontmorillonite added to the same paint as A at 6 dry lbs/100 gallonspaint was found to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     92,000 eps.                                                10 RPM             19,400 cps.                                                100 RPM             3,648 cps.                                                Krebs Stormer Viscosity                                                                          109 KU                                                     ICI Cone and Plate Viscosity                                                                     0.9                                                        Leneta Chart                                                                  Sag Reading        10                                                         Leveling Reading   4                                                          pH                 8.61                                                       Temp. °C    23.5                                                       Pounds/Gallons     11.95 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.65                                                       Scrub Rating       101/136                                                                       101/152                                                    Brush Drag Rating  3                                                          Brush Out Rating   OK Loading                                                                    Poor Leveling                                              Roller Splatter Rating                                                                           8                                                          Spray Out Rating   Good Atomization at 18 mils.                               Roll Out Rating    5 Splatter                                                                    Coarse Texture                                             ______________________________________                                    

D. An aqueous slurry of non-exchanged montmorillonite added to paint ata rate of 6 dry lbs/100 gallons paint was found to have the followingcharacteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     104,000 cps.                                               10 RPM              28,400 cps.                                               100 RPM             4.470 cps.                                                Krebs Stormer Viscosity                                                                          115 KU                                                     ICI Cone and Plate Viscosity                                                                     0.9                                                        Leneta Chart                                                                  Sag Reading        14                                                         Leveling Reading   1-2                                                        pH                 8.17                                                       Temp. °C.   22.6                                                       Pounds/Gallons     11.77 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.85                                                       Scrub Rating       166/200                                                                       137/216                                                    Brush Drag Rating  2.5                                                        Brush Out Rating   Good Loading                                               Roller Splatter Rating                                                                           7-8                                                        Spray Out Rating   Good Atomization at 16 mils.                               Roll Out Rating    4 Splatter                                                                    Fine Texture                                               ______________________________________                                    

E. An aqueous slurry of montmorillonite exchanged with the quat ACAR94005 (prepared as in Example 1, at 30 milliequivalence/100 gramsmontmorillonite) added to the same paint as D at 7 dry lbs/100 gallonspaint was found to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     81,600 cps.                                                10 RPM             16,360 cps.                                                100 RPM             2,840 cps.                                                Krebs Stormer Viscosity                                                                          101 KU                                                     ICI Cone and Plate Viscosity                                                                     0.8                                                        Leneta Chart                                                                  Sag Reading        8-9                                                        Leveling Reading   3                                                          pH                 8.24                                                       Temp. °C    22.6                                                       Pounds/Gallons     11.95 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.79                                                       Scrub Rating       154/183                                                                       122/159                                                    Brush Drag Rating  2.5-3                                                      Brush Out Rating   Good Loading                                               Roller Splatter Rating                                                                           8                                                          Spray Out Rating   Good Atomization at 17 mils.                               Roll Out Rating    2 Splatter                                                                    Fine Texture                                               ______________________________________                                    

F. An aqueous slurry of montmorillonite exchanged with the quat ACAR94005 (prepared as in Example 1, at 30 milliequivalence/100 gramsmontmorillonite) added to the same paint as D at 8 dry lbs/100 gallonspaint was found to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     127,000 cps.                                               10 RPM              34,260 cps.                                               100 RPM             6,280 cps.                                                Krebs Stormer Viscosity                                                                          132 KU                                                     ICI Cone and Plate Viscosity                                                                     1.1                                                        Leneta Chart                                                                  Sag Reading        16                                                         Leveling Reading   1                                                          pH                 8.21                                                       Temp. °C    22.8                                                       Pounds/Gallons     11.84 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.32                                                       Scrub Rating       137/154                                                                       103/167                                                    Brush Drag Rating  2.5-3                                                      Brush Out Rating   Good Loading                                               Roller Splatter Rating                                                                           9                                                          Spray Out Rating   Good Atomization at 18 mils.                               Roll Out Rating    5 Splatter                                                                    Fine Texture                                               ______________________________________                                    

G. An aqueous slurry of montmorillonite exchanged with the quat ACAR94006 (prepared as in Example 2 at 20 milliequivalence/100 gramsmontmorillonite) added to the paint at 6 dry lbs/100 gallons paint wasfound to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     130,000 cps.                                               10 RPM              27,000 cps.                                               100 RPM             4,640 cps.                                                Krebs Stormer Viscosity                                                                          118 KU                                                     ICI Cone and Plate Viscosity                                                                     0.9                                                        Leneta Chart                                                                  Sag Reading        12-13                                                      Leveling Reading   2                                                          pH                 8.18                                                       Temp. °C.   22.7                                                       Pounds/Gallons     11.90 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.67                                                       Scrub Rating       165/197                                                                       177/208                                                    Brush Drag Rating  2.5-3                                                      Brush Out Rating   Good Loading                                               Roller Splatter Rating                                                                           8-9                                                        Spray Out Rating   Good Atomization at 20 mils.                               Roll Out Rating    2 Splatter                                                                    Medium Texture                                             ______________________________________                                    

H. An aqueous slurry of montmorillonite exchanged with the quat ACAR94006 (prepared as in Example 2 at 20 milliequivalence/100 gramsmontmorillonite) added to the paint at 6 dry lbs/100 gallons paint wasfound to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     81,000 cps.                                                10 RPM             23,100 cps.                                                100 RPM             4,290 cps.                                                Krebs Stormer Viscosity                                                                          114 KU                                                     ICI Cone and Plate Viscosity                                                                     0.9                                                        Leneta Chart                                                                  Sag Reading        12                                                         Leveling Reading   2-3                                                        pH                 8.30                                                       Temp. °C.   22.6                                                       Pounds/Gallons     11.88 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.72                                                       Scrub Rating       182/236                                                                       170/220                                                    Brush Drag Rating  3                                                          Brush Out Rating   OK Loading                                                 Roller Splatter Rating                                                                           7-8                                                        Spray Out Rating   Good Atomization at 25-30 mils.                            Roll Out Rating    3 Splatter                                                                    Medium Texture                                             ______________________________________                                    

I. An aqueous slurry of montmorillonite exchanged with the quat ACAR94006 (prepared as in Example 2 at 20 milliequivalence/100 gramsmontmorillonite) added to the paint at 7 dry lbs/100 gallons paint wasfound to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                     121,000 cps.                                               10 RPM              37,400 cps.                                               100 RPM             6,900 cps.                                                Krebs Stormer Viscosity                                                                          136 KU                                                     ICI Cone and Plate Viscosity                                                                     1.1                                                        Leneta Chart                                                                  Sag Reading        18                                                         Leveling Reading   1                                                          pH                 8.23                                                       Temp. °C.   22.5                                                       Pounds/Gallons     11.81 weight/gallon                                        Syneresis Settling Rating                                                     120/10D %          1.61                                                       Scrub Rating       145/196                                                                       157/196                                                    Brush Drag Rating  3.5                                                        Brush Out Rating   Ex. Loading                                                Roller Splatter Rating                                                                           8-9                                                        Spray Out Rating   Good Atomization at 18 mils.                               Roll Out Rating    5 Splatter                                                                    Medium Texture                                             ______________________________________                                    

J. An aqueous slurry of montmorillonite exchanged with the quat ACAR94005 (prepared as in Example 1 at 30 milliequivalence/100 gramsmontmorillonite) added to the paint at 7 dry lbs/100 gallons paint wasfound to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                    86,800 cps.                                                 10 RPM            17,880 cps.                                                 100 RPM            3,192 cps.                                                 Krebs Stormer Viscosity                                                                         100 KU                                                      ICI Cone and Plate Viscosity                                                                    0.8                                                         Leneta Chart                                                                  Sag Reading       10                                                          Leveling Reading  3                                                           pH                8.18                                                        Temp. °C.  23.0                                                        Pounds/Gallons    11.90 weight/gallon                                         Syneresis Settling Rating                                                     120/10 D %        1.61                                                        Scrub Rating      145/190                                                                       163/194                                                     Brush Drag Rating 2                                                           Brush Out Rating  OK Loading                                                                    Easy                                                        Roller Splatter Rating                                                                          9                                                           Spray Out Rating  Good Atomization at 16 mils.                                Roll Out Rating   5 Splatter                                                                    Rough Texture                                               ______________________________________                                    

K. An aqueous slurry of montmorillonite exchanged with the quat ACAR94006 (prepared as in Example 2 at 20 milliequivalence/100 gramsmontmorillonite) added to the paint at 5 dry lbs/100 gallons paint wasfound to have the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                    76,000 cps.                                                 10 RPM            15,520 cps.                                                 100 RPM            2,680 cps.                                                 Krebs Stormer Viscosity                                                                         95 KU                                                       ICI Cone and Plate Viscosity                                                                    0.8                                                         Leneta Chart                                                                  Sag Reading       10                                                          Leveling Reading  4                                                           pH                8.32                                                        Temp. °C.  22.7                                                        Pounds/Gallons    11.89 weight/gallon                                         Syneresis Settling Rating                                                     120/10D %         2.42                                                        Scrub Rating      131/197                                                                       160/200                                                     Brush Drag Rating 2                                                           Brush Out Rating  Ex. Loading                                                                   Easy                                                        Roller Splatter Rating                                                                          8                                                           Spray Out Rating  Good Atomization at 19 mils.                                Roll Out Rating   2 Splatter                                                                    Medium Splatter                                             ______________________________________                                    

L. Benjamin Moore Contractor Flat Enhance Vinyl Latex paint was found tohave the following characteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                    22,000 cps.                                                 10 RPM             6,960 cps.                                                 100 RPM            2,548 cps.                                                 Krebs Stormer Viscosity                                                                         102 KU                                                      ICI Cone and Plate Viscosity                                                                    1.1                                                         Leneta Chart                                                                  Sag Reading       8                                                           Leveling Reading  5                                                           pH                8.50                                                        Temp. °C.  23.6                                                        Pounds/Gallons    12.14 weight/gallon                                         Syneresis Settling Rating                                                     120/10D %         <1                                                          Scrub Rating      30/70                                                                         30/70                                                       Brush Drag Rating 4                                                           Brush Out Rating  Good Loading                                                                  Leveling OK                                                 Roller Splatter Rating                                                                          9                                                           Spray Out Rating  Fair Atomization at 12 mils.                                Roll Out Rating   5 Splatter                                                                    Leveling OK                                                 ______________________________________                                    

M. Benjamin Moore Regal Wall Satin paint was found to have the followingcharacteristics:

    ______________________________________                                        Brookfield Viscosity                                                          1 RPM (rotations per minute)                                                                    20,800 cps.                                                 10 RPM             4,500 cps.                                                 100 RPM            1,420 cps.                                                 Krebs Stormer Viscosity                                                                         87 KU                                                       ICI Cone and Plate Viscosity                                                                    1.4                                                         Leneta Chart                                                                  Sag Reading       15                                                          Leveling Reading  7                                                           pH                7.54                                                        Temp. °C.  23.3                                                        Pounds/Gallons    10.82 weight/gallon                                         Syneresis Settling Rating                                                     120/10D %         <1                                                          Scrub Rating      130/180                                                                       130/180                                                     Brush Drag Rating 2                                                           Brush Out Rating  Good Loading                                                                  Leveling OK                                                 Roller Splatter Rating                                                                          7                                                           Spray Out Rating  Fair Atomization at 12 mils.                                Roll Out Rating   5 Splatter                                                                    Leveling OK                                                 ______________________________________                                    

N. Benjamin Moore Contractor Flat with added paint was found to have thefollowing characteristics:

    ______________________________________                                        Krebs Stormer Viscosity 97 KU                                                 ICI Cone and Plate Viscosity                                                                           1.5                                                  Leneta Chart            10                                                    Sag Reading                                                                   ______________________________________                                    

Slight color change when comparing sealed leneta chart drawdown versusunsealed leneta chart drawdown.

O. Benjamin Moore paint with added tint was found to have the followingcharacteristics:

    ______________________________________                                        Krebs Stormer Viscosity 100 KU                                                ICI Cone and Plate Viscosity                                                                           1.5                                                  Leneta Chart             18                                                   Sag Reading                                                                   ______________________________________                                    

Slight color change when comparing sealed leneta chart drawdown versusunsealed leneta chart drawdown.

P. Product of Example 2 with commercial antisplattering AssociativeThickener (Rohm & Haas) agent added.

    ______________________________________                                        ICI Cone and Plate Viscosity                                                                          1.2                                                   Roller Splatter Rating  8                                                     ______________________________________                                    

TEST METHODS

Sag and leveling were conducted on Leneta antisag bar and lenetaleveling bar on leneta form 7B.

What is claimed is:
 1. An organoclay composition comprising the reactionproduct of a smectite-type clay having an ion exchange capacity of atleast 50 meq. wt. per 100 g. clay (active basis), and an alkoxylatedquaternary ammonium compound having the following formula: ##STR5##wherein R₁ and R₂ are alike or different, and are selected from thegroup consisting of C₁ -C₈ alkyl, benzyl or 2-hydroxyethyl groups; R₃ isa C₁ -C₈ alkyl, benzyl or 2-hydroxyethyl group, or an alkoxylated chaincontaining 0-10 moles ethylene oxide and 3-15 moles of an alkylene oxideresidue selected from the group consisting of propylene oxide, butyleneoxide and mixtures thereof; and R₄ is an alkoxylated chain containing0-10 moles ethylene oxide and 3-15 moles of an alkylene oxide residueselected from the group consisting of propylene oxide, butylene oxideand mixtures thereof; and X is the salt anion.
 2. The compositionaccording to claim 1 wherein the alkoxylated quaternary ammoniumcompound of formula I has the formula wherein R₃ and R₄ are eachindependently an alkoxylated chain containing 1-5 moles ethylene oxideand 4-10 moles of an alkylene oxide residue selected from the groupconsisting of propylene oxide, and/or butylene oxide and mixturesthereof.
 3. The composition according to claim 2 wherein the alkoxylatedquaternary ammonium compound of formula I has the formula wherein R₃ andR₄ each contain the residue of 5 moles ethylene oxide and 5 molespropylene oxide.
 4. The composition according to claim 2 wherein thealkoxylated quaternary ammonium compound of formula I has the formulawherein R₃ and R₄ each contain the residue of 1 mole of ethylene oxideand 4 moles of propylene oxide.
 5. The composition according to claim 2wherein the alkoxylated quaternary ammonium compound of formula I hasthe formula wherein R₃ and R₄ each contain the residue of 1 moleethylene oxide and 5 moles each of propylene oxide and butylene oxide.6. The composition according to claim 1 wherein the alkoxylatedquaternary ammonium compound of the formula I has the formula whereinR₁, R₂, and R₃ are each a methyl group and R₄ is an alkoxylated chain.7. The composition according to claim 6 wherein the alkoxylatedquaternary ammonium compound of formula I has the formula wherein R₄ isan alkoxylated chain containing 1 mole ethylene oxide and 9 molespropylene oxide.
 8. The composition according to claim 6 wherein thealkoxylated quaternary ammonium compound of formula I has the formulawherein R₄ is an alkoxylated chain containing 1 mole ethylene oxide, 5moles propylene oxide, and 5 moles butylene oxide.
 9. A process for thepreparation of an organoclay composition comprising the reaction productof a smectite-type clay having an ion exchange capacity of at least 50meq. wt. per 100 g. clay (active basis), and an alkoxylated quaternaryammonium compound having the following formula: ##STR6## wherein R, andR₂ are alike or different, and are selected from the group consisting ofC₁ -C₈ alkyl, benzyl or 2-hydroxyethyl groups; R₃ is a C₁ -C₈ alkyl,benzyl or 2-hydroxyethyl group, or an alkoxylated chain containing 0-10moles ethylene oxide and 3-15 moles of an alkylene oxide residueselected from the group consisting of propylene oxide, butylene oxideand mixtures thereof; and R₄ is an alkoxylated chain containing 0-10moles ethylene oxide and 3-15 moles of an alkylene oxide residueselected from the group consisting of the propylene oxide, butyleneoxide and mixtures thereof; and X is the salt anion, which comprises:a)dispersing a smectite-type clay having an ion exchange capacity of atleast 50 meq. wt. per 100 g. clay, in an aqueous media; b) heating thedispersion of step (a) to a temperature in excess of 30° C.; c) addingto the heated dispersion of step (b) of a quaternary ammonium salt##STR7## wherein R₁ and R₂ are alike or different, and are selected fromthe group consisting of C₁ C₈ alkyl, benzyl or 2-hydroxyethyl groups; R₃is a C₁ -C₈ alkyl, benzyl or 2-hydroxyethyl group, or an alkoxylatedchain containing 0-10 moles ethylene oxide and 3-15 moles of an alkyleneoxide residue selected from the group consisting of propylene oxide,butylene oxide and mixtures thereof; and R₄ is an alkoxylated chaincontaining 0-10 moles ethylene oxide and 3-15 moles of an alkylene oxideresidue selected from the group consisting of propylene oxide, butyleneoxide and mixtures thereof; and X is the salt anion, in the desiredmilliequivalent ratio; and d) agitating oft he mixture of step (c) toeffect completion of the reaction.
 10. The process according to claim 9wherein the alkoxylated quaternary ammonium compound of formula I hasthe formula wherein the R₃ and R₄ substituents are each independently analkoxylated chain containing 1-5 moles ethylene oxide and 4-10 moles ofan alkylene oxide residue selected from the groups consisting ofpropylene oxide, butylene oxide, and mixtures thereof.
 11. The processaccording to claim 10 wherein the alkoxylated quaternary ammoniumcompound of formula I has the formula wherein R₃ and R₄ each contain theresidue of 5 moles ethylene oxide and 5 moles propylene oxide.
 12. Theprocess according to claim 10 wherein the alkoxylated quaternaryammonium compound of formula I has the formula wherein R₃ and R₄ eachcontain the residue of 1 mole of ethylene oxide and 4 moles of propyleneoxide.
 13. The process according to claim 10 wherein the alkoxylatedquaternary ammonium compound of formula I has the formula wherein R₃ andR₄ each contain the residue of 1 mole ethylene oxide and 5 moles each ofpropylene oxide and butylene oxide.
 14. The process according to claim 9wherein the alkoxylated quaternary ammonium compound of formula I hasthe formula wherein R₁, R₂, and R₈ are each a methyl group and R₄ is analkoxylated chain.
 15. The process according to claim 14 wherein thealkoxylated quaternary ammonium compound of formula I has the formulawherein R₄ is an alkoxylated chain containing 1 mole ethylene oxide and9 moles propylene oxide.
 16. The process according to claim 14 whereinthe alkoxylated quaternary ammonium compound of formula I has theformula wherein R₄ is an alkoxylated chain containing 1 mole ethyleneoxide, 5 moles propylene oxide, and 5 moles butylene oxide.